Subject Index 287
– oxy-Cope 188
– oxygen to carbon 234
–, propargylic, 1,3- 44
–, thermal 160, 162
reduction 21, 39
– of D-alkyl-E-ketoesters 21
– of E-ketoesters 26
– of 2,3,3-trimethyl-1-phenyl-1-butanone 25
– of DE-unsaturated carbene complexes 43
– with BH 3 ·py 21
– with lithium triethylborohydride
(LiEt 3 BH) 21
reductive elimination 42
regio- and stereochemistry 149
– of the [3+2] cycloaddition reactions
147f
regiochemistry 75, 147, 241
regioisomer 101, 200f
regioselectivity 33ff, 75, 103ff, 110,
197ff
– ortho/para 237
– of the reaction 201
regio-stereoselective 101
retention of the configuration 35ff, 235,
251, 254
retention of the optical activity 271
retention of the stereochemistry 234,
253ff, 272
Rh(II) carbene 140ff
–, intermediate 140
Rh(II) catalysts 141
–, decomposition with 139
ring closures, electrocyclic 159, 188
–, dearomatizing disrotatory 183
–, 6S disrotatory 161, 188
–, thermal 187
–, 8S conrotatory 161
ring closure, conrotatory six-electron 99
ring closure, photochemical 97f
ring openings, electrocyclic 159
ring-opening, epoxide 34f, 163
rotation around iminium C=N bond 180
rotation barrier 181, 255
rotation-isomerization 180
S
scrambling 270, 272
– of D/H 233f
– of deuterium 58ff, 232ff, 270, 275
– of the 2D-label 59
– of the D-label 56
– product 272
SDKIE 91, 238, 244ff
S E Ar-type substitution pathway 7
secondary D KIE see SDKIE
secondary effects 104
secondary F KIEs 244, 247
secondary KIE 91, 239f
secondary D- and E-D 88f
second-order kinetics 80
second-order rate constant 69
SET 107f, 111, 259f, 264ff
– mechanism 109, 266
shift, 1,2-H(D) 274
shift, 1,2-hydride 27, 274
short-lived intermediates 110
si-diastereoface 128
sigmatropic hydrogen shift, [1,5] 98f
sigmatropic rearrangement 97f
silane 128
(silylmethyl)phthalimides, N- 111
N N
silylnitronate 150
single electron transfer see SET
skeletal rearrangements 269
– in carbocations 275
slow step of the reaction 66, 173, 205,
215, 220, 240, 264
S N 1
–, mechanism 90, 94, 165
–, process 59
S N 2
– attack 192
– displacement 59, 73
– -like process 172
– mechanism 90, 233
– process 60, 93f, 115, 170f, 205f,
252
– type reaction 73, 93
S N Ar
– (addition-elimination) process 170
– mechanism 218, 241
– products 241
– reaction 217, 221, 241
SnCl 4 27, 125ff, 148
sodium methoxide 70
solvation 215
solvent
– -assisted D-elimination 234f
– -caged ion pair 28
– -dependent 59
– oxy-Cope 188
– oxygen to carbon 234
–, propargylic, 1,3- 44
–, thermal 160, 162
reduction 21, 39
– of D-alkyl-E-ketoesters 21
– of E-ketoesters 26
– of 2,3,3-trimethyl-1-phenyl-1-butanone 25
– of DE-unsaturated carbene complexes 43
– with BH 3 ·py 21
– with lithium triethylborohydride
(LiEt 3 BH) 21
reductive elimination 42
regio- and stereochemistry 149
– of the [3+2] cycloaddition reactions
147f
regiochemistry 75, 147, 241
regioisomer 101, 200f
regioselectivity 33ff, 75, 103ff, 110,
197ff
– ortho/para 237
– of the reaction 201
regio-stereoselective 101
retention of the configuration 35ff, 235,
251, 254
retention of the optical activity 271
retention of the stereochemistry 234,
253ff, 272
Rh(II) carbene 140ff
–, intermediate 140
Rh(II) catalysts 141
–, decomposition with 139
ring closures, electrocyclic 159, 188
–, dearomatizing disrotatory 183
–, 6S disrotatory 161, 188
–, thermal 187
–, 8S conrotatory 161
ring closure, conrotatory six-electron 99
ring closure, photochemical 97f
ring openings, electrocyclic 159
ring-opening, epoxide 34f, 163
rotation around iminium C=N bond 180
rotation barrier 181, 255
rotation-isomerization 180
S
scrambling 270, 272
– of D/H 233f
– of deuterium 58ff, 232ff, 270, 275
– of the 2D-label 59
– of the D-label 56
– product 272
SDKIE 91, 238, 244ff
S E Ar-type substitution pathway 7
secondary D KIE see SDKIE
secondary effects 104
secondary F KIEs 244, 247
secondary KIE 91, 239f
secondary D- and E-D 88f
second-order kinetics 80
second-order rate constant 69
SET 107f, 111, 259f, 264ff
– mechanism 109, 266
shift, 1,2-H(D) 274
shift, 1,2-hydride 27, 274
short-lived intermediates 110
si-diastereoface 128
sigmatropic hydrogen shift, [1,5] 98f
sigmatropic rearrangement 97f
silane 128
(silylmethyl)phthalimides, N- 111
N N
silylnitronate 150
single electron transfer see SET
skeletal rearrangements 269
– in carbocations 275
slow step of the reaction 66, 173, 205,
215, 220, 240, 264
S N 1
–, mechanism 90, 94, 165
–, process 59
S N 2
– attack 192
– displacement 59, 73
– -like process 172
– mechanism 90, 233
– process 60, 93f, 115, 170f, 205f,
252
– type reaction 73, 93
S N Ar
– (addition-elimination) process 170
– mechanism 218, 241
– products 241
– reaction 217, 221, 241
SnCl 4 27, 125ff, 148
sodium methoxide 70
solvation 215
solvent
– -assisted D-elimination 234f
– -caged ion pair 28
– -dependent 59